Hard and easy sinterable B4C-TiB2-based composites doped with WC

B₄C-TiB₂ composites were contaminated with WC to study the effect on densification, microstructure and properties. WC was introduced through a mild or a high energy milling with WC-6?wt%Co spheres or directly as sintering aid to 50?vol% B₄C / 50?vol%TiB₂ mixtures. High energy milling was very effective in improving the densification thanks to the synergistic action of WC impurities, acting as sintering aid, and size reduction of the starting TiB₂-B₄C powders. As a result, the sintering temperature necessary for full densification decreased to 1860?°C and both strength and hardness benefited from the microstructure refinement, 860?±?40 MPa and 28.5?±?1.4?GPa respectively. High energy milling was then adopted for producing 75?vol% B₄C/25?vol% TiB₂ and 25?vol% B₄C/ 75vol%TiB₂ mixtures. The B₄C-rich composition showed the highest hardness, 32.2?±?1.8?GPa, whilst the TiB₂-rich composition showed the highest value of toughness, 5.1?±?0.1?MPa?m^0.5.     

Microstructure and mechanical behaviour of transient liquid phase spark plasma sintered B4C–SiC–TiB2 composites from a B4C–TiSi2 system

Almost fully-dense B₄C–SiC–TiB₂ composites with a high combination of strength and toughness were prepared through in situ reactive spark plasma sintering using B₄C and TiSi₂ as raw materials. The densification, microstructure, mechanical properties, reaction, and toughening mechanisms were explored. TiSi₂ was confirmed as a reactive sintering additive to promote densification via transient liquid-phase sintering. Specifically, Si formed via the reaction between B₄C and TiSi₂ that served as a transient component contributed to densification when it melted and then reacted with C to yield more SiC. Toughening mechanisms, including crack deflection, branching and bridging, could be observed due to the residual stresses induced by the thermoelastic mismatches. Particularly, the introduced SiC–TiB₂ agglomerates composed of interlocked SiC and TiB₂ played a critical role in improving toughness. Accordingly, the B₄C–SiC–TiB₂ composite created with B₄C-16 wt% TiSi₂ achieved excellent mechanical performance, containing a Vickers hardness of 33.5 GPa, a flexural strength of 608.7 MPa and a fracture toughness of 6.43 MPa m^1/2.     

Dense and core-rim structured B4C-TiB2 ceramics with Mo-Co-WC additive

B₄C-TiB₂ ceramics (TiB₂ ranging 5~70 vol%) with Mo-Co-WC as the sintering additive were prepared by spark plasma sintering. In comparison with B₄C-TiB₂ without additive, the enhanced densification was evident in the sintered specimen with Mo-Co-WC additive. Core-rim structured grain was observed around TiB₂ grains. The interface of the rim between TiB₂ and B₄C phases demonstrated different feature: the inner borderline of the rim exhibited a smooth feature, whereas a sharp curved grain boundary was observed between the rim and the B₄C grain. The formation mechanism is discussed: the epitaxial growth of (Ti,Mo,W)B₂ rim around the TiB₂ core may occur as a result of the solid solution and dissolution-precipitation between TiB₂ phase and the sintering additive. It was revealed that the fracture toughness increased as the content of TiB₂ content increased, alongside the decreased hardness. B₄C-30 vol% TiB₂ specimen demonstrated the optimal combination of mechanical properties, reaching Vickers hardness of 24.3 GPa and fracture toughness of 3.33 MPa·m^1/2.     

High hardness and high fracture toughness B4C-diamond ceramics obtained by high-pressure sintering

The B₄C-diamond composite with high hardness and toughness was first prepared by high-pressure sintering of B₄C and diamond powders at 5 GPa and 1600 °C. The effect of the diamond fraction on the densification, microstructure and mechanical properties of B₄C-diamond composite were investigated. The results indicated that the hardness of the as-prepared composite ceramics increased gradually with the increase in diamond content. The composite having 40 vol% diamond exhibited excellent comprehensive mechanical properties with a relative density of 98.3%, a density of 2.86 g/cm³, Vickers hardness of 39.8 GPa and fracture toughness of 8.1 MPa·m^1/2. The use of superhard diamond enhanced the fracture toughness of the B₄C while maintaining its lightweight and high hardness. The main toughening mechanisms were crack bridging, crack deflection and pull-out of homogeneously dispersed diamond grains. Superhard second phase dispersion high-pressure sintering provides a new technical route to improve the properties of advanced composites.     

B4C‒TiB2 composite with modified microstructure and enhanced properties from optimal size coupling of raw powders

B₄C‒15 vol% TiB₂ composites were fabricated by in situ reactive spark plasma sintering with B₄C, TiC, and amorphous B powders as the raw materials. The size coupling of initial B₄C and TiC particles was optimized based on the reaction mechanism to derive B₄C‒TiB₂ composites with enhanced microstructure and properties. During the reactive sintering, fine B₄C–TiB₂ particles were firstly formed by an in situ reaction between TiC and B. Then, large B₄C particles tended to grow at the cost of small B₄C particles. The in situ TiB₂ grains gradually grew up and interconnect, distributing around the large B₄C grains to form an intergranular TiB₂ network. The results showed that the B₄C‒15 vol% TiB₂ composite prepared from 3.12 μm B₄C powder and 0.80 μm TiC powder had the optimal comprehensive properties, with a relative density of 99.50%, a Vickers hardness of 31.84 GPa, a flexural strength of 780 MPa, a fracture toughness of 5.77 MPa·m^1/2, as well as an electrical resistivity of 3.01 × 10⁻² Ω·cm.     

Fabrication of toughened B4C composites with high electrical conductivity using MAX phase as a novel sintering aid

MAX phase Ti₃AlC₂ was chosen as a novel sintering aid to prepare electrically conductive B₄C composites with high strength and toughness. Dense B₄C composites can be obtained at a hot-pressing temperature as low as 1850 °C with 15 vol% Ti₃AlC₂. The enhanced sinterability was mainly ascribed to the in situ reactions between B₄C and Ti₃AlC₂ as well as the liquid phase decomposed from Ti₃AlC₂. Both the Vickers hardness and fracture toughness increase with increasing Ti₃AlC₂ amount, and high hardness and toughness values of 28.5 GPa and 7.02 MPa m^−1/2 respectively were achieved for B₄C composites sintered with 20 vol% Ti₃AlC₂ at 1900 °C. Crack deflection by homogenously distributed TiB₂ particles was identified as the main toughening mechanism. Besides, B₄C composites sintered with Ti₃AlC₂ show significantly improved electrical conductivity due to the percolation of highly conductive TiB₂ phase, which could enhance the machinability of B₄C composites largely by allowing electrical discharge machining.     

Enhancement mechanical properties of in-situ preparated B4C-based composites with small amount of (Ti3SiC2+Si)

B₄C-based composites were synthesized by spark plasma sintering using B₄C、Ti₃SiC₂、Si as starting materials. The effects of sintering temperature and second phase content on mechanical performance and microstructure of composites were studied. Full dense B₄C-based composites were obtained at a low sintering temperature of 1800 °C. The B₄C-based composite with 10 wt% (TiB₂+SiC) shows excellent mechanical properties: the Vickers hardness, fracture toughness, and flexural strength are 33 GPa, 8 MPa m^1/2, 569 MPa, respectively. High hardness and flexural strength were attributed to the high relative density and grain refinement, the high fracture toughness was owing to the crack deflection and uniform distribution of the second phase.     

Transition metal diboride-silicon carbide-boron carbide ceramics with super-high hardness and strength

Three phase boride and carbide ceramics were found to have remarkably high hardness values. Six different compositions were produced by hot pressing ternary mixtures of Group IVB transition metal diborides, SiC, and B₄C. Vickers’ hardness at 9.8 N was ~31 GPa for a ceramic containing 70 vol% TiB₂, 15 vol% SiC, and 15 vol% B₄C, increasing to ~33 GPa for a ceramic containing equal volume fractions of the three constituents. Hardness values for the ceramics containing ZrB₂ and HfB₂ were ~30% and 20% lower than the corresponding TiB₂ containing ceramics, respectively. Hardness values also increased as indentation load decreased due to the indentation size effect. At an indentation load of 0.49 N, the hardness of the previously reported ceramic containing equal volume fractions of TiB₂, SiC and B₄C was ~54 GPa, the highest of the ceramics in the present study and higher than the hardness values reported for so-called “superhard” ceramics at comparable indentation loads. The previously reported ceramic containing 70 vol% TiB₂, 15 vol% SiC, and 15 vol% B₄C also displayed the highest flexural strength of ~1.3 GPa and fracture toughness of 5.7 MPa·m^1/2, decreasing to ~0.9 GPa and 4.5 MPa·m^1/2 for a ceramic containing equal volume fractions of the constituents.     

High-strength TiB2-B4C composite ceramics sintered by spark plasma sintering

Spark plasma sintering (SPS) is an advanced sintering technique because of its fast sintering speed and short dwelling time. In this study, TiB₂, Y₂O₃, Al₂O₃, and different contents of B₄C were used as the raw materials to synthesize TiB₂-B₄C composites ceramics at 1850°C under a uniaxial loading of 48 MPa for 10 min via SPS in vacuum. The influence of different B₄C content on the microstructure and mechanical properties of TiB₂-B₄C composites ceramics are explored. The experimental results show that TiB₂-B₄C composite ceramic achieves relatively good comprehensive properties and exceptionally excellent flexural strength when the addition amount of B₄C reaches 10 wt.%. Its relative density, Vickers hardness, fracture toughness, and flexural strength reach to 99.20%, 24.65 ± .66 GPa, 3.16 MPa·m^1/2, 730.65 ± 74.11 MPa, respectively.     

B4C–TiB2 composites fabricated by hot pressing TiC–B mixtures: The effect of B excess

Previous research have reported that B₄C–TiB₂ composites could be prepared by the reactive sintering of TiC–B powder mixtures. However, due to spontaneous oxidation of raw powders, using TiC–B powder mixtures with a B/TiC molar ratio of 6: 1 introduced an intermediate phase of C during the sintering process, which deteriorated the hardness of the composites. In this report, the effects of B excess on the phase composition, microstructure, and mechanical properties of B₄C–TiB₂ composites fabricated by reactive hot pressing TiC–B powder mixtures were investigated. XRD and Raman spectra confirmed that lattice expansion occurred in B-rich boron carbide and B_xC–TiB₂ (x > 4) composites were obtained. The increasing B content improved the hardness and fracture toughness but decreased the flexural strength of B_xC–TiB₂ (x > 4) composites. When the molar ratio of B/TiC increased from 6.6:1 to 7.8:1, the Vickers hardness and the fracture toughness of the composites were enhanced from 26.7 GPa and 4.53 MPa m^1/2 to 30.4 GPa and 5.78 MPa m^1/2, respectively. The improved hardness was attributed to the microstructural improvement, while the toughening mechanism was crack deflection, crack bridging and crack branching.     

Investigation of the density and microstructure homogeneity of square-shaped B4C-ZrB2 composites produced by spark plasma sintering method

Square-shaped monolithic B₄C and B₄C-ZrB₂ composites were produced by spark plasma sintering (SPS) method to investigate the effect of 5, 10, 15 vol% ZrB₂ addition on the densification, mechanical and microstructural properties of boron carbide. The relative density of B₄C increased with the increasing volume fraction of ZrB₂ and density differences in different regions of the sample narrowed down. Homogeneous density distribution and microstructure were accomplished with the increasing holding time from 7 to 20 min for the B₄C-15 vol% ZrB₂ composites, and the highest overall relative density was achieved as 99.23%. The hardness and fracture toughness of composites were enhanced with the addition of ZrB₂ compared to monolithic B₄C. The enhancement in fracture toughness was observed due to the crack deflection, crack bridging and crack branching mechanisms. The B₄C-15 vol% ZrB₂ composite exhibited the combination of superior properties (hardness of 33.08 GPa, Vickers indentation fracture toughness of 3.82 MPa.m^1/2).     

Microstructure and properties of a graphene platelets toughened boron carbide composite ceramic by spark plasma sintering

A kind of B₄C/SiC composite ceramic toughened by graphene platelets and Al was fabricated by spark plasma sintering. The effects of graphene platelets and Al on densification, microstructure and mechanical properties were studied. The sintering temperature was decreased about 125–300?°C with the addition of 3–10?wt% Al. Al can also improve fracture toughness but decrease hardness. The B₄C/SiC composite ceramic with 3?wt%Al and 1.5?wt% graphene platelets sintered at 1825?°C for 5?min had the optimal performances. It was fully densified, and the Vickers hardness and fracture toughness were 30.09?±?0.39?GPa and 5.88?±?0.49?MPa?m^1/2, respectively. The fracture toughness was 25.6% higher than that of the composite without graphene platelets. The toughening mechanism of graphene platelets was also studied. Pulling-out of graphene platelets, crack deflection, bridging and branching contributed to the toughness enhancement of the B₄C-based ceramic.     

In situ synthesis and densification of submicrometer-grained B4C-TiB2 composites by pulsed electric current sintering

B₄C composites with 15 and 30 vol% TiB₂ were pulsed electric current sintered from B₄C-TiO₂-carbon black mixtures in vacuum at 2000 °C. Full densification could be realised when applying an optimized loading cycle in which the maximum load is applied after completion of the B₄C-TiB₂ powder synthesis, allowing degassing of volatile species. The influence of the sintering temperature on the phase constitution and microstructure during synthesis and densification was assessed from interrupted sintering cycles. The in situ conversion of TiO₂ to TiB₂ was a complex process in which TiO₂ is initially converted to TiB₂ with B₂O₃ as intermediate product at 1400-1700 °C. At 1900-2000 °C, B₂O₃ reacted with C forming B₄C and CO. The B₄C and TiB₂ grain size in the fully densified 30 vol% TiB₂ composite was 0.97 and 0.63 μm, combining a Vickers hardness of 39.3 GPa, an excellent flexural strength of 865 MPa, and modest fracture toughness of 3.0 MPa m^1/2.     

Preparation and mechanical properties of laminated B4C–TiB2/BN ceramics

Laminated B₄C–TiB₂ ceramics with h-BN interface layers were successfully prepared by roll forming and tape casting, and samples with different numbers of stacked layers were obtained. Scanning electron microscopy and X-ray diffraction were used to analyze the microstructure and interlayer crystal phases of the composites, and the bending strength, fracture toughness, and work of fracture were measured. As the number of h-BN layers increased, the fracture toughness increased from 7.38 ± 0.5 MPa m^1/2 to 9.01 ± 0.61 MPa m^1/2, which is 2–3 times higher than that of monolithic B₄C ceramics. As the fracture toughness increased, the hardness remained at a high level (31.67 GPa). Bending tests showed that cracks deflected when they encountered the h-BN interfacial layers. The toughening mechanisms included the deflection and branching of cracks and generation of new microcracks, which increased the length of the propagation path and work of fracture.     

Hard and tough ultrafine-grained B4C-cBN composites prepared by high-pressure sintering

Tough and hard ultrafine-grained B₄C-cBN composites were firstly fabricated by high-pressure sintering mixed B₄C and cBN nanopowders at 6 GPa and 1700 °C. The phase transition from cBN to hBN is avoided by high pressure during the sintering process. The effects of the cBN content on the densification and mechanical properties of B₄C-cBN composites were evaluated. The results indicated that the hardness of the as-fabricated composites increased gradually with the increase of cBN content. The composite composed of 50 wt.% cBN exhibited excellent comprehensive mechanical properties with relative density of 98.6 %, density of 2.9 g/cm³, Vickers hardness of 36.2 GPa and fracture toughness of 6.7 MPa·m^1/2. The introduction of superhard cBN maintained the lightweight and high hardness while enhancing the fracture toughness of the B₄C. The main toughening mechanisms were crack bridging, crack deflection and pull-out of homogeneously dispersed cBN grains.     

Synthesis and properties of conductive B4C ceramic composites with TiB2 grain network

High electrical resistance and low fracture toughness of B₄C ceramics are 2 of the primary challenges for further machining of B₄C ceramics. This report illustrates that these 2 challenges can be overcome simultaneously using core‐shell B₄C‐TiB₂&TiC powder composites, which were prepared by molten‐salt method using B₄C (10 ± 0.6 μm) and Ti powders as raw materials without co‐ball milling. Finally, the near completely dense (98%) B₄C‐TiB₂ interlayer ceramic composites were successfully fabricated by subsequent pulsed electric current sintering (PECS). The uniform conductive coating on the surface of B₄C particles improved the mass transport by electro‐migration in PECS and thus enhanced the sinterability of the composites at a comparatively low temperature of 1700°C. The mechanical, electrical and thermal properties of the ceramic composites were investigated. The interconnected conductive TiB₂ phase at the grain boundary of B₄C significantly improved the properties of B₄C‐TiB₂ ceramic composites: in the case of B₄C‐29.8 vol% TiB₂ composite, the fracture toughness of 4.38 MPa·m^1/2, the electrical conductivity of 4.06 × 10⁵ S/m, and a high thermal conductivity of 33 W/mK were achieved.     

B4C–(Ti0.9Cr0.1)B2 composites with excellent specific hardness and enhanced toughness

Dense and light B₄C–(Ti_0.9Cr_0.1)B₂ composites with excellent mechanical properties were designed and reactively densified from boron, TiC, and Cr₃C₂ powder mixtures by spark plasma sintering in this work. Due to solid solution effects, the as-obtained B₄C–(Ti_0.9Cr_0.1)B₂ composite exhibited obviously enhanced hardness (43.2 ± 3.0 GPa at 9.8 N) and higher specific hardness (12.82 GPa cm³ g⁻¹) together with improved flexural strength (663 ± 39 MPa) and fracture toughness (K_IC, 5.40 ± 0.25 MPa m^1/2), compared to the counterparts such as B₄C–TiB₂ composite and B₄C. Toughening contributions in the as-sintered ceramics were quantitatively analyzed, and higher K_IC in B₄C–(Ti_0.9Cr_0.1)B₂ was mainly due to their larger initial fracture toughness and compressive stress toughening. The combination of these properties makes B₄C–(Ti_0.9Cr_0.1)B₂ composites exhibit great potentials in the application as lightweight structural materials. This work provided an inspiration to achieve lightweight materials with high performance through doping minor-amount atoms into the matrix.     

Microstructures and mechanical properties of B4C–SiC and B4C–SiC–TiB2 ceramic composites fabricated by hot pressing

Boron carbide (B₄C) ceramic composites with excellent mechanical properties were fabricated by hot-pressing using B₄C, silicon carbide (SiC), titanium boride (TiB₂), and magnesium aluminum silicate (MAS) as raw materials. The influences of SiC and TiB₂ content on the microstructural evolution and mechanical properties of the composites were systematically investigated. The mechanism by which MAS promotes the sintering process of composites was also investigated. MAS exists in composites in the form of amorphous phase. It can effectively remove the oxide layer from the surface of ceramic particles during the high temperature sintering process. The typical values of relative density, hardness, bending strength, and fracture toughness of B₄C–SiC–TiB₂ composites are 99.6%, 32.61 GPa, 434 MPa, and 6.20 MPa m^1/2, respectively. Based on the microstructure observations and finite element modeling, the operative toughening mechanism is mainly attributed to the crack deflection along the grain boundary, which results from the residual stress field generated by the thermal expansion mismatch between B₄C and TiB₂ phase.     

Effect of graphite content on properties of B4C‐W2B5 ceramic composites by in situ reaction of B‐Gr‐WC

Strip‐shaped W₂B₅ reinforced B₄C ceramic composites were prepared via in situ reaction of boron(B)‐graphite(Gr)‐WC system by powder metallurgy (P/M). In order to study the effect of the graphite content on the properties of the as‐fabricated ceramic composites, the powder mixture of B‐Gr‐WC with various amounts of Gr powder were blended and consolidated by spark plasma sintering (SPS). The sintering parameters were shown as following: sintering pressure was set as 30 MPa; The three‐step sintering temperature was 1100‐1550‐1700°C and the duration time was set as 5‐5‐6 minutes, respectively. In situ formed strip‐shaped W₂B₅ particles were dispersed homogeneously in B₄C matrix, which resulted in a remarkable improvement on the fracture toughness and mechanical properties. Appropriate 5vol% residual Gr in the composite shows positive effect on the mechanical properties which achieved an optimal counter‐balance of fracture toughness and hardness, the relative density was 99.8%, the Vickers hardness can reach 30.2 GPa, and the fracture toughness was 11.9 MPa·m^1/2 when the sintering temperature was set at 1700°C.     

Toughening of SiC matrix with in-situ created TiB2 particles

SiC–TiB₂ composites with up to 50 vol% TiB₂ were fabricated by in-situ reaction between TiO₂, B₄C and C. The densification of the uniaxially pressed samples was done using pressureless sintering in the presence of sintering aids consisting of Al₂O₃ and Y₂O₃. The influence of the volume fraction of TiB₂ and sintering temperature on density and fracture toughness was examined. It was found that fracture toughness is strongly affected by the volume fraction of TiB₂. The presence of TiB₂ particles suppresses the grain growth of SiC and facilitates different toughening mechanisms to operate which, in turn, increases fracture toughness of the composite. The highest value for fracture toughness of 5.7 MPa m^1/2 was measured in samples with 30 vol% TiB₂ sintered at 1940 °C.